Method of activating clays



Oct. 3, 1939. J. w. wElR IETBOD OF ACTIVATI-NG'CL-YS Filed Feb. 2'?,1939 GM. ww W 55mm, l. m l

Patented ocr. 3, 1939 UNITED STAT-Es PATENT OFFICE one-third to HenryPasadena, Calif.

S. Montgomery, South Application February 27, 1939, Serial No.`25.8,73'1

2 Claims.

This invention relates to a process of activating clays and has for itsobject both to improve and increase the decolorizing, refining,catalytic,

clarifying, purifying, and adsorptive properties 5 of clay or kindredsubstances when hydrocarbon tion the word clay is used in a broad senseand is meant to comprise and include the substances known as bauxite,willonite, pyrophyllite, kaolinite', fullers earth, montmorillonite,diatomaceous earth, lbentonite, green sands, premutite, barromite,heulandite, phyllipsite, hormatone,

' stillbite or desmine, laumontite, chabazite, analcite, -natrolite,scolesite, thompsonite, aluminum silicate clays, magnesium clays,leverrierite, Wyoming rock clays, Otai clays, Death Valley claysincluding both the aluminum silicate and magnesium silicate types, andkindred substances, whether asnaturally mined or after a previous use ofthe clay.

Another object of this invention is the production of activated clay,which is a new composition of matter, from clays having little orsubstantially no practical value as an activated clay. This newproduc-t, which is unlike others, is the result of the use of differentchemicals, applied in adifferent way, in different proportions, in adifferent chemical state, in a different physical state, whereindifferent reactions occur,`different compounds are formed, differentreaction compounds are removed, therefore, there remains a new residualmaterial.

The words activated clay as herein used shall be construed to mean andinclude substances and activated materials having decolorizing, re-

ning, catalytic, clarifying, purifying, neutralizing, or adsorptiveproperties, when liquid hydrocarbons, petroleum oils, vegetable oils,animal oils, waxes, fats, sugar solutions, and all liquids capable ofbeing refined or treated with such a material are contacted therewith oriiltered therethrough.

Another object of this invention is to utilize any available gas orvapor which may be manufactured from any suitable material or by-productor otherwise produced, as'a cheap source of supply of chemicalsapplicable to the process, and especially to utilize the by-products ofindustrial chemical manufacturing plants, smelters, refineries, etc.,which said by-products are generally inert, for the successfultreatments of clays. As stated, the gases above referred to aregenerally inert to the treatment of clays, but when combined with othergases or with other reagents as (ci. 25a-z) 4herein described, theybecome active by this in-A vention.

Another object of this invention is to make possible the use of gaseousor liquid substances which are of themselves inert or substantially sofor the treatment of clays and by the methods employed as hereindescribed to become chemically reactive to clay.

Examples of such substances are sulphur dioxide, hydrogen, hydrogensulphide, chlorine, the oxides of nitrogen, steam and water.

By inert chemically to clay as used in the specifications and claims ofthis invention, it is means that the reagent or substancereferred to andemployed is ineiective in the treatment of clays to produce a good gradeof decolorizing material.

By this invention a combination of more than one of the above namedtypes of substances is employed in the step of applying the chemicals tothe clay under treatment, examples of which are the followingcombinations and methods which may be employed in applying the varioussubstances mentioned. This new method of application causes the employedsubstances to become active and eilicient chemical reagents in thetreatment of clays.

Combinations and methods of application are:

Sulphur dioxide and chlorine 1. The two gases are introduced into anaqueous solution containing clay simultaneously and concurrently untilthe required amount of the chemicals is added to treat the clay in thesolution.

2. Sulphur dioxide 'is introduced into an aqueous solution containingclay until the required amount of sulphur dioxide is dissolved in same,being sullicient to treat the clay present-in the solution. Chlorine isthen introduced till the desired treatment is accomplished.

3. To a required quantity of Water to make a solution with a desiredweight of clay dissolve the required quantity of sulphur dioxide beforethe'clay is added to the solution. Then add the desired quantity of clayto the water-sulphurdioxide solution. Then introduce chlorine into thesaid solution y containing the clay until the desired treatment isaccomplished.

The above sequence of introducing the gases into the solution may bereversed in order of procedure; that is to say, the chlorine may be usediirst in the series of steps followed by the sulphur dioxide. This alsoapplies to all other combinations of two or more gases employed in theprocess, such as hydrogen sulphide, sulphur dioxide, and chlorine.

It is understood that the order of procedure and the sequence of allsteps may be changed and reversed in the operation and the applicationof this process and such steps are meant l 1 to be included inthespecication and claims of this invention.

Chlorine and hydrogen Chlorine and hydrogen sulphide The two gases maybe introduced into an aqueous solution containing clay.

Sulphur dioide and the oxides of nitrogen The plurality of gasesisintroduced, in the presence of steam, into an aqueous solution conltaining clay.

This invention, for the purposes herein recited, comprises and includesthe use of gaseous substances andr any plurality of gaseous substancesof the group, sulphur dioxide, hydrogen sulphide, chlorine, the oxidesof nitrogen, hydrogen, steam, and all gases which will chemicallyinter-react with each other in the combinations as employed in thepresence of an aqueous solution containing clay, and will chemicallyreact upon the said clay and cause an improvement in the quality of thetreated clay product as an activated clay over the untreated clay.

In the process gases may be introduced into the solution employedthrough separate conduits without admixture or through pre-mixingchambers, inter-mixed therein before entering the solution. Suchsubstances as HC1 gas and S03 Vapor are each good active treatingreagents for clays when used alone and introduced into an aqueoussolution containing clay.

By using this invention activated clay may be produced of a betterquality than the best standard brand on themarket and equal to the bestdecolorizing material that, to our knowledge, can be made by any knowntreating process. This statement is made after having produced such amaterial and submitting it to comparable tests.

The reason and theory is thought to be tha the superior quality of thefinished product is the result of using reagentsthat inter-react to formactive reagents in the presence of the clay and While in a nascent statereact with the clay. By the term nascent I mean that the activefreagentsas formed are in a lightly ionized and reactive state.

When the words burning of sulphur are used in the specification andclaims of this invention, it is meant to include the burning of allsubstancescontaining sulphur whichmay be burned to produce sulphurdioxide, including hydrogen lsulphide in the non-condensable gases fromrening or destructive distillation of petroleum or coal and itsproducts.

In the accompanying diagrammatic drawing v is illustrated an apparatussuitable for demonstrating the manufacture of sulphur dioxide from theburning of sulphurtor substances containing combined sulphur, and theproduction of chlorine from salt by electrolysis or from other sources,and the method of their use by this invention and referring to the saiddrawing.`

Approximatelyv eight parts by weightof water through pipe I is run intomixer 2, one part by weight, of clay from crusher 3, is run into Waterin mixer 2, while being agitated with stirring paddle 4, until reducedto a finely divided condition, which` then passes through pipe 1 23,into treating tanks 5 and 6 to fully charge them in equal quantitieswhile being agitated with paddles 8 and 9.

The two treating tanks 5 and B are connected in a reversible series, andas here illustrated, tank 6 is theprimary treating tank and treatingtank 5, as a secondary treating tank, is acting to absorb any excess ofeither gas inadvertently introduced into treating tank which throughsolution containing clay under treatment, passes out through pipe I9into treating tank 5, into the solution therein lcontaining clay, whereby manipulating the manifold pipe arrangement, valves not shown, eitherchlorine through pipe 2|, or sulphur dioxide through pipe 22 may beintroduced into said treating tank 5 and into said solution to maintaina proper proportionate ratio between the gases in the said solution toreact with any such aforementioned excess gas in the presence of theclay in the said solution. This regulation to maintain the properproportions of gases as employed is continuous during the operations.

The primary treating tank. 6, as-above shown, contains clay in a iinelydivided condition dispersed in water and under agitation, and inreadiness for the treating step which follows in this describedembodiment of this invention, and comprises the use of two gases whichare introduced simultaneously and concurrently into the said treatingtank 6.

One of the said two gases is chlorine, which, coming from electrolyticcell II) by compressor II, is introduced through pipe I2 into primarytreating tank 6.

The other of the said two `gases is the combustion gas containingsulphur dioxide coming from the burning of sulphur or substancescontaining combined sulphur, which is fed by automatic feeder I3 intorotary burner I4 from whence the combustion gases pass throughcombustion chamber I5, air cooler I6, compressor I1, which through pipeIintroduce's it into said primary treating tank AI5.

By regulating the rate of flow of the above tw gases entering treatingtank 6, they are intermixed in the proper proportions to chemicallyinterreact with each other and while in a nascent state, react with theclay under treatment in the aqueous solution, and the ilow of 'gases iscontinued until the desired predetermined quantity of the two gases isdelivered to effect the desired treatment of the clay. The quantity ofthe two gases used depends upon whether a high or low treatment isdesired, that is, whether a high grade or low grade product is requiredto meetl the consumer demand. The excess or partly spent gas or vaporpasses out of the treating tank li, through pipe I9, into treating tank5, through solution therein containing clay and the waste gases pass outthrough loaded valve and Vent 2D. When treatment of the clay in thesolution in treating` tank Ii is complete, the proper valves, not

shown, are opened and closed and the chlorine4 Then the solutioncontaining the clay is withdrawn from digester 36, through pipe 4I, andby conventional and well-known methods not described, reaction productsare removed from the clay and the treated product is prepared fordisposition in any preferred manner. y

As above illustrated, normal pressures and temperatures were employed upto the digestion step in digester 36.

`In the shell stank type apparatus as indicated in` drawing, and withcompressors as shown,

pressures up to one hundred pounds or more could be used, and higherpressures and'templete is the interreaction between the substancesemployed and the reaction with the. clay under treatment.

It is understood that, for the purposes herein recited, the scope ofthis invention shall comprise and include operations at all pressuresand from low to high temperatures.

The word gas or gases as herein employed is meant to mean and includeall substances herein employed that are gases or vapors at normalpressure and temperature. f

At low temperatures the preferred substances employed in this inventionmay become liquids or solids and at normal temperature may be held in aliquid state under pressure.

Therefore, this invention', for the purposes herein recited, comprisesand includes the use of sulphur dioxide and chlorine in the mannerherein describedv in all forms, gaseous, liquid, solid, and in aqueoussolutions.

In one ofthe preferred embodiments of this invention sulphur dioxide isemployed in an aqueous solution into which clay is added, then chlorineis introduced into the said aqueous sulphur dioxide solution containingclay, where inter-reaction takes place between the chlorine and thesulphur dioxide and a reaction occurs with the clay present therein.

The aqueous sulphur dioxide solution may come from any source to be usedas such in the process, .or it may be made in any preferred manner, suchas by absorbing in water sulphur dioxide from the combustion gases ofburning sulphur, or by adding it to water in-a gaseous, liquid, or solidform.

This may be considered as treating the clay'with the liquid sulphurousacid. Sulphur dioxide, sulphurous acid, and aqueous solutions of sulphurdioxide are not good active treating reagents forv clay and only becomeso when chlorine, or some substance that wiii react'with it, is added asherein described.

A new and novel feature of this invention,

which is meant to be comprised and included therein, is the'use ofeither or both gaseous or liquid substances that are inert chemically toclay, and in the process it is only necessary to f have ,the clayparticles sumciently small to perployed to make a uniform and thoroughtreatment of the clay.

In the solutions of the treating step the amount of water used inproportion to the clay present may vary in wide proportions from a veryliquid condition of the clay to a mass comparatively dry, but still ofsu'icient water content to insure no loss of active reagents, that is tosay, the water content of the clay may vary through awide range Withoutdetrimental aiect upon the .clay treatment, care being taken not toover-saturate the mixture with reagents due to lack of water.

The words in an aqueous solution are meant to include solutions of allproportions with reference to the relative Weights of water to clay inthe solutions employed. It is not meant that the clay is in solution. Itis meant that the clay vis present in a solution or moist condition inwhich the water or moisture present is suiicient to bring aboutinter-reactions between the substances employed and a reaction with theclay present under treatment.

' The following is a second illustration of methods of carrying out theinvention.

Referring to drawing:

To avoid repetition will assume that the sulphur burner is in operation.

Treating tanks 6 and 5 are charged with solution containing clay underagitation.

Combustion gases from the burning'of sulphur of approximately 10%sulphur dioxide content are delivered by compressor II through pipe I8`into an aqueous solution containing approximately eight parts Water andone part clay, by weight, in treating tank Ii, until approximately 6% byweight based upon clay present in the solution, is absorbed therein. Thepartially spent mit intimate contact with the substances emgases passout through pipe I9, through solution sorber 26, for striping of sulphurdioxide. A

Then chlorine from ele'ctrolyticv cell III, by com-v pressor Il, throughpipe I2, is introduced into clay-sulphur-dioxide solution in treating6,;v

until desired treatment isf completed.

Then the treated clay in the` solutio11- -from i treating tank' 6 istransferred throughpipe-3lv into digester 36, where during agitationwith stir@ .i-

ring paddle 38,V steam heat is vapplied until' 'by boiling 25% to50%,'.of thewater content is evapof rated, or until reaction is completewith the clay.'

'I'hen the treated claynrthe solutionis with-:-

drawn through vpipe I I 'andwater-solublereae--. tion products removedtherefrorn'and.- the'treated `1 product is prepared; for disposalinany-,prferred-Q 1J The followingis a third'illustratioriiof"nietlitklsv 1 manner.

of carrying outthe process.

Referring to the drawing:l

Sulphur introduced through. automaticfoe'der 1 v I3 is burned in rotaryburner il, combustion chamber I5, to about 10% sulphur dioxide contentin combustion gases which is pumped with compressor I1, through absorber26, line 2T, and

absorber 28, Waste gases escaping through loaded l valve and vent 34. l

During this operation water is being circulated counter-current to saidcombustion gases by introducing water through pipe 29 into top ofabsorber 28 out by pump 30, through pipe 42, into top of absorber 26,out by pump 3|Y through pipe 32, into sulphur dioxide solution tank 33.

Approximately eight parts of water to one of clay, by weight, may beused in treating the clay in the solution. v6% by weight of sulphurdioxide, approximately, is required to treat the clay (based on weightof clay).

Therefore, from sulphur dioxide solution tank 33, through pump 34, pipe35, sufficient sulphur dioxide solution is delivered into mixer 2, thesulphur dioxide content of' which will equal 6% of the weight of theclay to be treated. Then through pipe I, add sufficient Water into mixer2 to make the aqueous solution content eight parts by weight of the clayto be treated in same.l

, Then from crusher 3, during agitation with stir- 4bring about thedesired reactions.

ring paddle 4, one part of clay is run4 into the` eight partsV ofsolution in mixer 2 and the clay in the aqueous sulphur dioxide solutionis reduced to nely divided condition. Then from mixer 2 thesulphur-dioxide-clay-solution through pipes -1 and 23, is run in equalquantities into treating `tanks 5 and 6 during agitation with stirringpaddles 8 and 9. Then chlorine from electrolytic cell I0, by compressorll, through line I2, is introduced into treating tank 6 into thesulphur-di-Y oxide-clay-solution, the partially spent gas passingthrough pipe I9 into treating tank 5 throughsulphur-dioxide-clay-solution, the waste gas passing out through vent20. ment is completed, the chlorine is switched through pipes I 2 2!into treating tank 5, and yfrom tank 6 the solution containing thetreated clay is transferred through pipe .31 to digester 36, duringagitation with paddle y38, and steam heat is applied until 25% to 50% ofthe water in the solution is evaporated, or until the reaction Vwith theclay is complete.

Then the treated clay in the solution is Withdrawn through pipe 4l andwater soluble reaction products removed therefrom-and the treated whichare in direct ratio to the combining molecuarweight of the substancesemployed. Any

excess over such quantities is lost if the excess ofl the substanceemployed has not a further and additional beneficial effect upon theclay under treatment.

4For example in the use of chlorine and sulphur dioxide, thefproportions -required in the inter- .yeaccio'n one lg,re70.92 parts ofchlorine and 64.06 partsof Asulphur dioxide, by weight, and foreilifilent','results conditionsumust be maintained. to

contact .the substances in such proportions. Due tothe complex reactionsas brought about by this invention, an excess of either of these twosubstances may react as bleaching agents or otherwise to contribute tothe superior quality of the nished treated product.

When the treaty In practicing this invention, minimum quantities of allthe substances, including water, employed in the process may be moreeiciently applied by the use of high temperatures and pressures. Highltemperatures are meant to mean and include temperatures above thenormal boilingpoints oi the aqueous solutions of the substancesemployed, and up to the critical temperature which may be applied to theapparatus under operating conditions. meant to include pressuressuicient to maintain, at the existing temperature, the aqueous solutionsemployed in the liquid phase to at least such an extent that the vaporphase present is the smaller portion as comparedto the liquid phase.Such pressures may be as high as 2,000 pounds per square inch.

In the acid treatment of hydrocarbonoils the acid reaction product iscalled acid sludge.

There arenumerous processes employed in the refining art of recoveringfrom the acid sludge, the acid used in treating, examples of which are:

l. Water or steam is added to the sludge and heat is applied and thesolution is allowed to settle when it generally 'straties into three.

phases, the upper being oil, the middle being tar, the lower a weak acidsolution. The Weak acid solution is generally concentrated by heat orconventional methods or stronger acid. During all `heating applicationssulphur dioxide is generated which may be collected for use or disposal.

2. The sludge is heated in a closed retort, rotary internal type retort,or in any conventional manner in the presence of air or oxygen whereby aresidual fuel of any state of dryness may be produced, sulphur dioxideis generated, a part or all .of the volatile matter is vaporized, and.the intermixed air, sulphur dioxide and High pressures are;

vapor coming 01T together pass through a condenser where the condensablevapors are liqueed and removed' and the remaining gases are passedthrough scrubbing, purifying, or burning steps, after which the sulphurdioxide may be absorbed in water, separated therefrom. and

liquefied or converted into S03 or H2804 by any. of the well knownmethods.

The use of the sulphur dioxide and gases containing sulphur dioxidegenerated as above indicated is meant -to be included and covered bythis invention.

It is understood that this invention is not limited to the detailsherein described as preferred embodiments of 'the same and suchernbodlments are intended by way of example only, but this invention isof the scope dened in the specications and the following claims.

I claim as my invention:

1. In the process of activating clay, the improvement in the method ofapplying activating agents, which comprises,v contacting comminuted claysuspended ln water, with sulfur dioxide and lchlorine gas, and` finallyseparating activate clay from soluble products of reaction. Y 2. In theprocess of activating clay, the improvement inv the ymethod of applyingactivating agents, which comprises contacting comminuted clay in a watersuspension, with sulfur dioxide and chlorine gas, forming sulfuric andhydrochloric acids in a highly ionized state, immediately reacting onthe suspended clay with the ionized acids as generated and nallyseparating activated clay from Water soluble products of reaction.

JAMES W. WEIR.

